JP5323308B2 - Light emitting module - Google Patents
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- JP5323308B2 JP5323308B2 JP2006252742A JP2006252742A JP5323308B2 JP 5323308 B2 JP5323308 B2 JP 5323308B2 JP 2006252742 A JP2006252742 A JP 2006252742A JP 2006252742 A JP2006252742 A JP 2006252742A JP 5323308 B2 JP5323308 B2 JP 5323308B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 105
- 239000004065 semiconductor Substances 0.000 claims description 23
- 229910052586 apatite Inorganic materials 0.000 claims description 13
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 13
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 12
- 235000011180 diphosphates Nutrition 0.000 claims description 12
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- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 230000003595 spectral effect Effects 0.000 claims description 5
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- 238000000295 emission spectrum Methods 0.000 description 17
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- 229910052693 Europium Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
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- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
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- H01L2224/45144—Gold (Au) as principal constituent
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
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Description
本発明は、高輝度で演色性に優れた橙色蛍光体を用いた発光モジュールに関する。 The present invention relates to a light emitting module using an orange phosphor having high luminance and excellent color rendering.
環境問題や省電力の観点から水銀を使用しない、発光ダイオード(LED)や半導体レーザー(LD)を励起光源として蛍光体と組み合わせ、そのときの発光を光源とし、消費電力の少ない照明用光源が開発されている。
例えば、特許文献1には、LEDから発せられる青色光と青色系の発光の一部を吸収して発光するCe付活希土類アルミン酸塩蛍光体からの黄色系の発光との加色混合によって全体として白色系の発光を呈する発光ダイオードが開示されている。しかしながら、この組み合わせのタイプは、最終的に得られる白色光の発光色が限定され、また本光源の照明下での色の再現性が好ましい色に再現されず、演色性に問題があった。また、発光ダイオードからの発光の光路上に設置される蛍光体の量のばらつきにより、青色光、黄色光の比率が安定せず、発光モジュールの発光色が安定しない問題もあった。
In light of environmental issues and power savings, light source diodes (LEDs) and semiconductor lasers (LDs) that do not use mercury are combined with phosphors as excitation light sources, and light sources at that time are used as light sources. Has been.
For example, Patent Document 1 discloses that blue light emitted from an LED and yellow light emitted from a Ce-activated rare earth aluminate phosphor that absorbs a part of blue light and emits light are mixed. As a light emitting diode, a white light emitting diode is disclosed. However, this type of combination has a problem in color rendering properties because the emission color of white light finally obtained is limited, and color reproducibility under illumination of this light source is not reproduced in a preferable color. In addition, there is a problem in that the ratio of the blue light and the yellow light is not stable due to the variation in the amount of phosphors installed on the optical path of light emitted from the light emitting diode, and the light emission color of the light emitting module is not stable.
近年、このような問題を解決するため、2色加色での白色合成の欠点を補う方法として、紫外又は短波長可視光を半導体発光素子からの一次光(励起光)とし、緑・青・赤3成分の蛍光体を混合する(加法混色)ことによる発光モジュールが紹介されている(例えば、特許文献2参照。)。ここでは、青色発光蛍光体としてBaMgAl10O17:Eu2+(以降、BAMとも称する) 、(Sr、Ca、Ba)5(PO4)3Cl:Eu2+等、緑色発光蛍光体としてCa8Mg(SiO4)4Cl:Eu2+,Mn2+、BaMgAl10O17:Eu2+,Mn2+等、赤色発光蛍光体としてはY2O2S:Eu3+(YOS:Eu)、Y2O3:Eu,Bi、La2O2S:Eu3+(LOS:Eu)等が挙げられている。 In recent years, in order to solve such problems, as a method for compensating for the disadvantages of white synthesis by adding two colors, ultraviolet or short-wavelength visible light is used as primary light (excitation light) from a semiconductor light emitting device, and green, blue, A light emitting module by mixing phosphors of three red components (additive color mixture) has been introduced (see, for example, Patent Document 2). Here, BaMgAl 10 O 17 : Eu 2+ (hereinafter also referred to as BAM) is used as the blue-emitting phosphor. , (Sr, Ca, Ba) 5 (PO 4 ) 3 Cl: Eu 2+, etc., such as Ca 8 Mg (SiO 4 ) 4 Cl: Eu 2+ , Mn 2+ , BaMgAl 10 O 17 : Eu As red emitting phosphors such as 2+ and Mn 2+ , Y 2 O 2 S: Eu 3+ (YOS: Eu), Y 2 O 3 : Eu, Bi, La 2 O 2 S: Eu 3+ (LOS: Eu) and the like.
しかし、赤・緑・青各色を発光する蛍光体の中でも、赤色発光蛍光体は、緑・青各色を発光する蛍光体に比べて発光効率が低いため、所望の白色(例えば、色度x/y=0.360/0.365)を得るには、この赤色発光蛍光体を、緑・青各色を発光する蛍光体よりも混合割合を多目に、例えば配合比を90%近くにしなければならなかった。このため、発光効率の良好な緑・青色発光蛍光体の配合比が低くなり、発光モジュールとして高輝度の白色を発光するものが得られなかった。 However, among the phosphors that emit red, green, and blue colors, the red light-emitting phosphor has lower luminous efficiency than the phosphor that emits each color of green and blue, so that a desired white color (for example, chromaticity x / In order to obtain y = 0.360 / 0.365), this red light emitting phosphor must be mixed in a larger proportion than the phosphors emitting green and blue colors, for example, the mixing ratio should be close to 90%. did not become. For this reason, the compounding ratio of the green / blue light-emitting phosphors having good luminous efficiency is low, and a light emitting module that emits white with high luminance cannot be obtained.
前記従来の赤色発光蛍光体の中でも、LOS:Eu(以降LOSとも称する)は「21世紀の明かり」プロジェクトで開発され、現在最も優れた赤色発光体であり、赤色発光蛍光体の標準品ともされている。
しかし、その励起ピーク波長が340nmであり、紫外線LEDチップの最高出力波長(400nm)とかけ離れており、400nmの励起光では十分に満足できる明るさの発光が得られないことが問題になっていた。
Among the conventional red light-emitting phosphors, LOS: Eu (hereinafter also referred to as LOS) was developed in the “21st Century Light” project and is currently the most excellent red light-emitting phosphor, and is also regarded as a standard product of red light-emitting phosphors. ing.
However, the excitation peak wavelength is 340 nm, which is far from the maximum output wavelength (400 nm) of the ultraviolet LED chip, and it has been a problem that light emission with sufficiently satisfactory brightness cannot be obtained with 400 nm excitation light. .
また、LOSの発光スペクトルは624nmにシャープな発光ピークを有するものであり、このような赤色発光蛍光体を用いた加法混色による白色発光モジュールは充分な演色性が得られなかった。 Further, the emission spectrum of LOS has a sharp emission peak at 624 nm, and a white light emitting module using additive color mixture using such a red light emitting phosphor cannot obtain sufficient color rendering.
従って、本発明の目的は、上記問題点を解決することであり、従来の赤色発光蛍光体に代って、白色発光モジュールに用いた場合に高輝度で演色性に優れたものとすることができる発光蛍光体を用いた発光モジュールを提供することである。 Accordingly, an object of the present invention is to solve the above-described problems, and to provide high luminance and excellent color rendering when used in a white light emitting module instead of a conventional red light emitting phosphor. Another object is to provide a light emitting module using a light emitting phosphor.
本発明者らは、鋭意検討を重ねた結果、以下の構成を採用することによって、上記目的が達成され、本発明を成すに至った。 As a result of intensive studies, the present inventors have achieved the above object by adopting the following configuration, and have achieved the present invention.
(1)発光ピーク波長が350〜420nmである半導体素子と、前記半導体素子からの光を励起光源として発光する蛍光体層を備える発光モジュールであって、前記蛍光体層は、少なくとも下記一般式で表されるα型Caピロリン酸塩結晶構造を有する橙色蛍光体を含むことを特徴とする発光モジュール。
Ca2-X-Y-ZMXP2O7:EuY,MnZ
(式中、MはCa以外のアルカリ土類元素を表し、X≧0、Y>0、Z>0である。)
(2)前記蛍光体層が前記橙色蛍光体と、少なくとも1種の別色の蛍光体を含んでおり、白色発光することを特徴とする(1)に記載の発光モジュール。
(3)前記一般式において、0.01≦Y≦0.3、0.01≦Z≦0.3であることを特徴とする(1)または(2)に記載の発光モジュール。
(4)前記一般式において、0.2≦Z/Y+Z≦0.8であることを特徴とする(1)〜(3)のいずれか1項に記載の発光モジュール。
(5)青色発光蛍光体と緑色発光蛍光体のうちいずれかの蛍光体と前記橙色蛍光体とを含み、白色発光することを特徴とする(2)〜(4)のいずれか1項に記載の発光モジュール。
(6)前記青色蛍光体がCaアパタイトであることを特徴とする(5)に記載の発光モジュール。
(1) A light emitting module comprising a semiconductor element having an emission peak wavelength of 350 to 420 nm and a phosphor layer that emits light from the semiconductor element as an excitation light source, wherein the phosphor layer is represented by the following general formula: A light emitting module comprising an orange phosphor having an α-type Ca pyrophosphate crystal structure.
Ca 2-XYZ M X P 2 O 7: Eu Y, Mn Z
(In the formula, M represents an alkaline earth element other than Ca, and X ≧ 0, Y> 0, and Z> 0.)
(2) The light emitting module according to (1), wherein the phosphor layer includes the orange phosphor and at least one different color phosphor and emits white light.
(3) The light emitting module according to (1) or (2), wherein in the general formula, 0.01 ≦ Y ≦ 0.3 and 0.01 ≦ Z ≦ 0.3.
(4) The light emitting module according to any one of (1) to (3), wherein 0.2 ≦ Z / Y + Z ≦ 0.8 in the general formula.
(5) Any one of the blue light-emitting phosphor and the green light-emitting phosphor and the orange phosphor, and emits white light, according to any one of (2) to (4) Light emitting module.
(6) The light emitting module according to (5), wherein the blue phosphor is Ca apatite.
本発明の発光モジュールの蛍光体層に含まれる橙色蛍光体は、(1)励起スペクトルのピーク波長が紫外線LEDチップの最高出力波長域である400nm付近にあり、(2)発光ピーク波長が赤色より視感度の高い600nmであり、(3)発光(積分)強度が従来のLOSよりも大きいことにより、発光モジュールに用いた場合、高輝度のものを得ることができるなどの性質を有する。
また、本発明の発光モジュールの蛍光体層に含まれる橙色発光体は(4)発光スペクトルがブロードであるため、発光モジュールに用いた場合、演色性に優れたものとなる性質を有する。
The orange phosphor contained in the phosphor layer of the light emitting module of the present invention has (1) the peak wavelength of the excitation spectrum is in the vicinity of 400 nm, which is the maximum output wavelength region of the ultraviolet LED chip, and (2) the emission peak wavelength is from red. When it is used for a light emitting module, it has properties such that a high luminance can be obtained because it has a high visibility of 600 nm and (3) its emission (integration) intensity is higher than that of a conventional LOS.
Moreover, since the orange light emitter contained in the phosphor layer of the light emitting module of the present invention has a broad emission spectrum (4), it has a property of being excellent in color rendering when used in a light emitting module.
本発明の発光モジュールに含まれる橙色蛍光体は従来の赤色発光蛍光体よりも発光効率がよく、視感度および輝度が優れているため、高効率で輝度および演色性に優れたモジュールとすることができる。 Since the orange phosphor contained in the light emitting module of the present invention has higher luminous efficiency and better visibility and luminance than the conventional red light emitting phosphor, it should be a highly efficient module with excellent luminance and color rendering. it can.
本発明の発光モジュールに含まれる橙色蛍光体は、α型Caピロリン酸塩結晶構造を有し、下記一般式で表されることを特徴とするものである。 The orange phosphor contained in the light emitting module of the present invention has an α-type Ca pyrophosphate crystal structure and is represented by the following general formula.
Ca2-X-Y-ZMXP2O7:EuY,MnZ
(式中、MはCa以外のアルカリ土類元素を表し、X≧0、Y>0、Z>0である。)
Ca 2-XYZ M X P 2 O 7: Eu Y, Mn Z
(In the formula, M represents an alkaline earth element other than Ca, and X ≧ 0, Y> 0, and Z> 0.)
このような上記一般式で表される橙色蛍光体は、励起ピーク波長が350〜420nmであり、InGaN/GaN系半導体素子の外部量子効率の最大値が得られる390〜410nmを含んでいる。また、発光ピーク波長が600nm付近でかつブロードな発光スペクトルであるため、発光モジュールに用いた場合には、従来のものに比べ、輝度、演色性が改善された発光モジュールとすることができる。 Such an orange phosphor represented by the above general formula has an excitation peak wavelength of 350 to 420 nm, and includes 390 to 410 nm from which the maximum value of the external quantum efficiency of the InGaN / GaN-based semiconductor element can be obtained. In addition, since the emission peak wavelength is around 600 nm and the emission spectrum is broad, when used in a light emitting module, a light emitting module with improved luminance and color rendering can be obtained compared to the conventional one.
上記一般式で表される橙色蛍光体において、付活剤金属ユーロピウム(Eu)およびマンガン(Mn)の和Y+Zは、特に限定されないが、0.1〜0.6であることが好ましく、0.15〜0.45であるものがより好ましい。 In the orange phosphor represented by the above general formula, the sum Y + Z of the activator metals Europium (Eu) and Manganese (Mn) is not particularly limited, but is preferably 0.1 to 0.6. What is 15-0.45 is more preferable.
また、付活剤金属ユーロピウム(Eu)およびマンガン(Mn)の量はそれぞれ、0.01≦Y≦0.3、0.01≦Z≦0.3であることが好ましい。
さらに、上記一般式で表される橙色蛍光体において、総付活剤(Eu+Mn)中におけるMnの比率Z/Y+Zは、特に限定されないが、0.2〜0.8であることが好ましい。
The amounts of activator metals europium (Eu) and manganese (Mn) are preferably 0.01 ≦ Y ≦ 0.3 and 0.01 ≦ Z ≦ 0.3, respectively.
Furthermore, in the orange phosphor represented by the above general formula, the ratio of Mn Z / Y + Z in the total activator (Eu + Mn) is not particularly limited, but is preferably 0.2 to 0.8.
本発明の発光モジュールに用いられる橙色蛍光体は、特に限定されないが、粒径が50μm以下であることが好ましい。粒径が50μm以下であることにより、蛍光体の粒子表面における光の散乱を防ぐことができ、効率良く蛍光体を発光させることができる。 The orange phosphor used in the light emitting module of the present invention is not particularly limited, but preferably has a particle size of 50 μm or less. When the particle size is 50 μm or less, scattering of light on the particle surface of the phosphor can be prevented, and the phosphor can emit light efficiently.
本発明の発光モジュールは、他の色を発光する蛍光体を構成物として用いることもでき、例えば紫外線発光半導体素子と青・緑色発光蛍光体とを組み合わせて白色発光モジュールとすることができる。
この場合、橙色蛍光体以外に、基本的にはさらに青色発光蛍光体および緑色発光蛍光体を用いるものであるが、より望ましい、所望の色度の白色を得るためには、さらに他蛍光体を用いることも可能である。
The light emitting module of the present invention can also use phosphors emitting other colors as constituents. For example, an ultraviolet light emitting semiconductor element and a blue / green light emitting phosphor can be combined to form a white light emitting module.
In this case, in addition to the orange phosphor, basically, a blue light-emitting phosphor and a green light-emitting phosphor are used. However, in order to obtain a more desirable white color with a desired chromaticity, other phosphors are used. It is also possible to use it.
蛍光体として、橙色蛍光体(O)と緑色発光蛍光体(G)と青色発光蛍光体(B)のみを用いる場合には、それらの配合比率は、スペクトル分率比で、(O)35〜75:(G)15〜50:(B)2〜30であることが好ましく、より好ましくは、(O)45〜74:(G)20〜45:(B)5〜15である。 When only the orange phosphor (O), the green light-emitting phosphor (G), and the blue light-emitting phosphor (B) are used as the phosphor, the blending ratio thereof is a spectral fraction ratio, and (O) 35 to 35 It is preferable that it is 75: (G) 15-50: (B) 2-30, More preferably, it is (O) 45-74: (G) 20-45: (B) 5-15.
橙色蛍光体と共に用いられる青色発光蛍光体としては、発光ピーク波長が400〜500nmのものが好ましく、緑色発光蛍光体としては、発光ピーク波長が500〜550nmのものが好ましい。 The blue light-emitting phosphor used with the orange phosphor preferably has a light emission peak wavelength of 400 to 500 nm, and the green light-emitting phosphor preferably has a light emission peak wavelength of 500 to 550 nm.
青色発光蛍光体としては(CaMgEu)5(PO4)3Clで表されるCaアパタイト蛍光体、(SrEu)5(PO4)3Clで表されるSrアパタイト蛍光体、BAMなどが用いられるが、Caアパタイト蛍光体が好ましい。 Ca apatite phosphor as the blue-emitting phosphor represented by (CaMgEu) 5 (PO 4) 3 Cl, (SrEu) 5 (PO 4) 3 Sr apatite phosphor represented by Cl, the like BAM is used Ca apatite phosphors are preferred.
Caアパタイト蛍光体としては、好ましくは下記一般式で表される蛍光体である。
Ca5-X-YMgXEuY(PO4)3Cl
(0.05≦X≦2.5、0<Y<0.5)
The Ca apatite phosphor is preferably a phosphor represented by the following general formula.
Ca 5-XY Mg X Eu Y (PO 4 ) 3 Cl
(0.05 ≦ X ≦ 2.5, 0 <Y <0.5)
緑色発光蛍光体としては、SrAl2O4:Euで表されるSrアルミネート蛍光体、(Sr1−X―Y―ZBaxCaYEuz)2SiO4で表される(Sr,Ba)オルソ・シリケイト系蛍光体およびSrGaS4:Euで表されるSrチオガレート蛍光体、BAM:EuMn蛍光体を用いる。 As the green light emitting phosphor, Sr aluminate phosphor represented by SrAl 2 O 4 : Eu, (Sr 1-XYZ Ba x Ca Y Eu z ) 2 SiO 4 (Sr, Ba ) An ortho-silicate phosphor, a Sr thiogallate phosphor represented by SrGaS 4 : Eu, and a BAM: EuMn phosphor are used.
また、本発明の発光モジュールに用いられる橙色蛍光体と併用して、従来より公知公用の赤色発光蛍光体、橙色蛍光体も適宜使用できる。
公知公用の赤色蛍光体としては、本明細書の背景技術に記載のものが挙げられる。
そして、発光モジュールに必須に橙色蛍光体と、併用しうる青色発光蛍光体、緑色発光蛍光体、公知公用の赤色発光蛍光体、橙色蛍光体は、紫外線耐性のものが好ましい。
Further, in combination with the orange phosphor used in the light emitting module of the present invention, conventionally known and publicly available red light emitting phosphors and orange phosphors can be used as appropriate.
The publicly known red phosphors include those described in the background art of this specification.
In addition, the blue phosphor, the green phosphor, the publicly known red phosphor, and the orange phosphor that can be used in combination with the orange phosphor essential for the light emitting module are preferably UV-resistant.
橙色蛍光体を用いる本発明の発光モジュールに用いられる半導体発光素子としては、発光ピーク波長が350〜420nmであれば、特に限定されないが、紫外線を発光する半導体発光素子として一般的なInGaN/GaN系のものが好ましい。詳細には、特開2002−17100号公報に記載されているもの等が好適に使用できる。
InGaN/GaN系の半導体発光素子は、In量が多くなるほど発光ピーク波長が長くなり、In量が減るほど発光ピーク波長が短くなる。よって、InGaN/GaN系の半導体発光素子を発光モジュールに適用するためには、その発光ピーク波長が350〜420nmになるように、Inの量を適宜調整する。
The semiconductor light-emitting element used in the light-emitting module of the present invention using an orange phosphor is not particularly limited as long as the emission peak wavelength is 350 to 420 nm, but is generally an InGaN / GaN-based semiconductor light-emitting element that emits ultraviolet light. Are preferred. Specifically, those described in JP-A-2002-17100 can be suitably used.
In an InGaN / GaN-based semiconductor light emitting device, the emission peak wavelength becomes longer as the In amount increases, and the emission peak wavelength becomes shorter as the In amount decreases. Therefore, in order to apply the InGaN / GaN-based semiconductor light emitting device to the light emitting module, the amount of In is adjusted as appropriate so that the emission peak wavelength becomes 350 to 420 nm.
本発明の発光モジュールは、前記の半導体発光素子と橙色蛍光体を含む蛍光体とから構成されるものであるが、より具体的には、該半導体発光素子上に該蛍光体の層を設ける構成が挙げられる。
その場合、半導体発光素子上に設ける該蛍光体層は、少なくとも1種以上の蛍光体を単層又は複数層を層状に積層配置しても良いし、複数の蛍光体を単一の層内に混合して配置しても良い。上記半導体発光素子上に蛍光体層を設ける形態としては、半導体発光素子の表面を被覆するコーティング部材に蛍光体を混合する形態、モールド部材に蛍光体を混合する形態、或いはモールド部材に被せる被覆体に蛍光体を混合する形態、更には半導体発光素子ランプの投光側前方に蛍光体を混合した透光可能なプレートを配置する形態等が挙げられる。モールド部材に混合する場合には、耐UV特性の良好なシリコーン樹脂内に分散していることが好ましい。
The light emitting module of the present invention is composed of the semiconductor light emitting element and a phosphor containing an orange phosphor. More specifically, the phosphor layer is provided on the semiconductor light emitting element. Is mentioned.
In that case, the phosphor layer provided on the semiconductor light emitting element may be a single layer or a plurality of layers in which at least one kind of phosphor is laminated and a plurality of phosphors are arranged in a single layer. You may mix and arrange | position. As a form in which the phosphor layer is provided on the semiconductor light emitting element, a form in which the phosphor is mixed with a coating member that covers the surface of the semiconductor light emitting element, a form in which the phosphor is mixed with the mold member, or a covering that covers the mold member And a mode in which a translucent plate in which the phosphor is mixed is disposed in front of the light emitting side of the semiconductor light emitting element lamp. When mixed in a mold member, it is preferably dispersed in a silicone resin having good UV resistance.
また、半導体発光素子上のモールド部材に、前述の蛍光体の少なくとも1種以上が添加されていても良い。更に、前述の蛍光体の少なくとも1種以上からなる蛍光体層を、発光モジュールの外側に設けても良い。発光モジュールの外側に設ける形態としては、発光モジュールのモールド部材の外側表面に蛍光体を層状に塗布する形態、或いは蛍光体をゴム、樹脂、エラストマー等に分散させた成形体(例えば、キャップ状)を作製し、これを半導体発光素子に被覆する形態、又は前記成形体を平板状に加工し、これを半導体発光素子の前方に配置する形態等が挙げられる。 In addition, at least one of the aforementioned phosphors may be added to the mold member on the semiconductor light emitting device. Furthermore, you may provide the fluorescent substance layer which consists of at least 1 sort (s) or more of the above-mentioned fluorescent substance on the outer side of a light emitting module. As a form provided on the outside of the light emitting module, a form in which the phosphor is applied in layers on the outer surface of the mold member of the light emitting module, or a molded body in which the phosphor is dispersed in rubber, resin, elastomer or the like (for example, cap shape) The form which coats this to a semiconductor light emitting element, or the form which processes the above-mentioned fabrication object in the shape of a plate, and arranges this in front of a semiconductor light emitting element, etc. are mentioned.
本発明の橙色蛍光体を用いる発光モジュールの具体的な形態の1例を図1に示す。図1に示す発光モジュールは、1のチップはInGaN活性層を有する中心波長が395nm付近の短波長可視光LEDチップであり、この短波長可視光LEDチップ1は接着剤層を介してリードフレーム2に固定されている。短波長可視光LEDチップ1とリードフレーム2は金線ワイヤー3により電気的に接続されている。前記短波長可視光LEDチップ1は、バインダー樹脂に蛍光体粉末を混練した蛍光体ペースト4で覆われている。この蛍光体ペースト4のバインダー樹脂は、シリコーン樹脂、エポキシ樹脂、ウレタン樹脂、ノルボルネン系樹脂、フッ素樹脂、金属アルコキシド、ポリシラザン、アクリル樹脂等が挙げられる。また、この発光モジュールは、この蛍光体ペースト4の周囲を覆う封止材5を有している。封止材5には、シリコーン樹脂、エポキシ樹脂、ウレタン樹脂、ノルボルネン系樹脂、フッ素樹脂、アクリル樹脂、低融点ガラス等の可視光に対し透明な材料が挙げられる。
なお、発光モジュール用の形態はこの発光モジュール構造に限定されるものではなく、例えば短波長可視光LEDチップ1の発光面に蛍光体層としてコーティングする等など、種々の形態がある。
An example of a specific form of a light emitting module using the orange phosphor of the present invention is shown in FIG. In the light emitting module shown in FIG. 1, one chip is a short wavelength visible light LED chip having an InGaN active layer and a center wavelength of around 395 nm. This short wavelength visible light LED chip 1 is connected to a lead frame 2 via an adhesive layer. It is fixed to. The short wavelength visible light LED chip 1 and the lead frame 2 are electrically connected by a gold wire 3. The short wavelength visible light LED chip 1 is covered with a phosphor paste 4 in which a phosphor powder is kneaded with a binder resin. Examples of the binder resin of the phosphor paste 4 include silicone resin, epoxy resin, urethane resin, norbornene resin, fluorine resin, metal alkoxide, polysilazane, and acrylic resin. In addition, the light emitting module has a sealing material 5 that covers the periphery of the phosphor paste 4. Examples of the sealing material 5 include materials that are transparent to visible light, such as silicone resin, epoxy resin, urethane resin, norbornene resin, fluorine resin, acrylic resin, and low-melting glass.
In addition, the form for light emitting modules is not limited to this light emitting module structure, For example, there exist various forms, such as coating the light emission surface of the short wavelength visible light LED chip 1 as a fluorescent substance layer.
本発明の発光モジュールを白色発光モジュールとする場合、所定の白色度を有することが好ましく、具体的にはJIS D 5500の車両用灯具の白色規定である、以下の数値規定範囲の通りであり、色度図で示すならば図2の網掛部に相当するものが好ましい。 When the light emitting module of the present invention is a white light emitting module, the light emitting module preferably has a predetermined whiteness, and specifically, the following is the numerical value defining range that is the white color regulation of the vehicle lamp of JIS D 5500, If shown in the chromaticity diagram, the one corresponding to the shaded portion in FIG.
黄方向 x≦0.50
青方向 x≧0.31
緑方向 y≦0.44 及び y≦0.15+0.64x
紫方向 y≧0.05+0.75x 及び y≧0.382
Yellow direction x ≦ 0.50
Blue direction x ≧ 0.31
Green direction y ≦ 0.44 and y ≦ 0.15 + 0.64x
Purple direction y ≧ 0.05 + 0.75x and y ≧ 0.382
より好ましい白色度規定範囲は、以下の通りであり、色度図で示すならば図3の網掛部に相当するものである。 A more preferable whiteness defining range is as follows, and if shown in the chromaticity diagram, it corresponds to the shaded portion of FIG.
0.310≦x≦0.405、かつ、黒体放射軌跡≦y≦0.15+0.64x 0.310 ≦ x ≦ 0.405 and blackbody radiation locus ≦ y ≦ 0.15 + 0.64x
本発明の橙色蛍光体を用いた白色発光モジュールの演色性について説明する。
演色性とは、測定光をサンプルに当てて得られる反射光の色が、サンプルの現実の色に対してどの程度近いのかを示す指標である。数値は最大値が100で値が大きいほど演色性が高い(良い)。具体的には、測定光をサンプル当てて得られる反射光の色が、サンプルの現実の色(理想の白色光を当てた場合の色)に対してどの程度近いのか(100がMAX)という値を、様々なサンプル(規定色)について測定し、その値の平均値をRaとするものである。
本発明の橙色蛍光体を用いた白色発光モジュールの演色性は、100に近いほど好ましいが、特に限定されるものではなく、望ましくは60以上である。
The color rendering properties of the white light emitting module using the orange phosphor of the present invention will be described.
The color rendering property is an index indicating how close the color of the reflected light obtained by applying the measurement light to the sample is with respect to the actual color of the sample. As for the numerical value, the maximum value is 100, and the larger the value is, the higher the color rendering is (good). Specifically, the value of how close the color of the reflected light obtained by applying the measurement light to the sample is relative to the actual color of the sample (the color when ideal white light is applied) (100 is MAX) Is measured for various samples (regular colors), and the average of the values is Ra.
The color rendering property of the white light emitting module using the orange phosphor of the present invention is preferably as close to 100, but is not particularly limited, and is desirably 60 or more.
以下に本発明を実施例によって更に具体的に説明するが、勿論本発明の範囲は、これらによって限定されるものではない。
[実施例1]
赤色蛍光体としてCaピロリン酸塩(Ca1.7Eu0.2Mn0.1)P2O7、緑色蛍光体としてBAM:Eu,Mn(化成オプトニクス社:KX−671)、青色蛍光体としてCaアパタイト((Ca4.67Mg0.25 Eu0.08)5(PO4)3Cl)を使用し、CIE色度(cx、cy)=(0.360、0.365)となるように混合したところ、スペクトル分率比54:38:8になった。この混合物をシリコン樹脂(東レ・ダウ・コーニング社:JCR6126)と1:1で混合したものを、200μm厚で光学ガラスに製膜し、150℃で1時間、硬化させ蛍光体フィルターを作製した。前記蛍光体フィルターをInGaN/GaN系半導体素子を用いた表面実装型発光モジュールの出射面に設置し、LEDを20mAで通電し、出射光の光束・演色性を評価した。その結果、平均演色指数(Ra)は84、全光束は比較例の1.9倍向上した。
The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples.
[Example 1]
Ca pyrophosphate (Ca 1.7 Eu 0.2 Mn 0.1 ) P 2 O 7 as red phosphor, BAM: Eu, Mn (Kasei Optonix: KX-671) as green phosphor, blue phosphor When Ca apatite ((Ca 4.67 Mg 0.25 Eu 0.08 ) 5 (PO 4 ) 3 Cl) is used as the mixture and mixed so that the CIE chromaticity (cx, cy) = (0.360, 0.365), the spectral fraction ratio 54: 38: 8. A mixture of this mixture and silicon resin (Toray Dow Corning: JCR6126) 1: 1 was formed into an optical glass with a thickness of 200 μm and cured at 150 ° C. for 1 hour to prepare a phosphor filter. The phosphor filter was placed on the exit surface of a surface-mount type light emitting module using an InGaN / GaN-based semiconductor element, the LED was energized at 20 mA, and the luminous flux and color rendering properties of the emitted light were evaluated. As a result, the average color rendering index (Ra) was 84, and the total luminous flux was improved 1.9 times that of the comparative example.
Caピロリン酸塩およびCaアパタイトは以下の方法により合成した。
[Caピロリン酸塩:(Ca1.7Eu0.2Mn0.1)P2O7の合成方法]
CaHPO4、Eu2O3、MnCO3および(NH4)H2PO4を1.7:0.1:0.1:0.3のモル比で計量した。均一に混合後、蓋付きアルミナ坩堝で1120〜1250℃の温度で、1〜3時間、H2を5%含むN2雰囲気下で焼成することにより合成した。
Ca pyrophosphate and Ca apatite were synthesized by the following method.
[Method of synthesizing Ca pyrophosphate: (Ca 1.7 Eu 0.2 Mn 0.1 ) P 2 O 7 ]
CaHPO 4 , Eu 2 O 3 , MnCO 3 and (NH 4 ) H 2 PO 4 were weighed in a molar ratio of 1.7: 0.1: 0.1: 0.3. After mixing uniformly, it was synthesized by firing in an alumina crucible with a lid at a temperature of 1120 to 1250 ° C. for 1 to 3 hours in an N 2 atmosphere containing 5% of H 2 .
[Caアパタイト:(Ca4.42Mg0.5Eu0.08)(PO4)3Clの合成方法]
CaCO3、MgCO3、Eu2O3、CaCl2およびCaHPO4を、0.17:0.5:0.04:1.25:3.0のモル比で計量した。均一に混合後、蓋付きアルミナ坩堝で1200℃の温度で、3時間、H2を5%含むN2雰囲気下で焼成することにより合成した。
[Method for synthesizing Ca apatite: (Ca 4.42 Mg 0.5 Eu 0.08 ) (PO 4 ) 3 Cl]
CaCO 3 , MgCO 3 , Eu 2 O 3 , CaCl 2 and CaHPO 4 were weighed at a molar ratio of 0.17: 0.5: 0.04: 1.25: 3.0. After mixing uniformly, it was synthesized by firing in an alumina crucible with a lid at a temperature of 1200 ° C. for 3 hours in an N 2 atmosphere containing 5% H 2 .
[実施例2]
赤色蛍光体としてCaピロリン酸塩(Ca1.7Eu0.2Mn0.1)P2O7、緑色蛍光体としてBAM:Eu,Mn(化成オプトニクス社:KX−671)、青色蛍光体としてSrアパタイト((SrEu)5(PO4)3Cl)(化成オプトニクス社:KX−663)を使用し、CIE色度(cx、cy)=(0.360、0.365)となるように混合したところ、スペクトル分率比52:39:9になった。以降実施例1と同様にして蛍光体フィルターを作製し、発光特性を評価したところ、Raは86、全光束比は、比較例の1.8倍向上した。
[Example 2]
Ca pyrophosphate (Ca 1.7 Eu 0.2 Mn 0.1 ) P 2 O 7 as red phosphor, BAM: Eu, Mn (Kasei Optonix: KX-671) as green phosphor, blue phosphor As Sr apatite ((SrEu) 5 (PO 4 ) 3 Cl) (Chemical Optonics KX-663), and mixed so that CIE chromaticity (cx, cy) = (0.360, 0.365) The spectral fraction ratio was 52: 39: 9. Thereafter, a phosphor filter was produced in the same manner as in Example 1, and the emission characteristics were evaluated. As a result, Ra was 86, and the total luminous flux ratio was 1.8 times that of the comparative example.
[比較例]
赤色蛍光体としてLOS(化成オプトニクス社:KX−681)、緑色蛍光体としてBAM:Eu,Mn(化成オプトニクス社:KX−671)、青色蛍光体としてBAM(化成オプトニクス社:KX−661)を使用し、CIE色度(cx、cy)=(0.360、0.365)を狙い混合したところ、スペクトル分率比66:26:8になった。以降、実施例1と同様にして蛍光体フィルターを作製し、発光特性を評価したところ、Raは37であった。
[実施例3〜12]
表1に示す組成で実施例1および2と同様に発光特性を測定した。用いた蛍光体中、Caピロリン酸塩およびLOSについては発光スペクトルおよび励起スペクトル、それ以外の蛍光体については発光スペクトルを図4〜14に示した。表1および図15〜図18に実施例および比較例の発光特性の評価の結果を示す。
[Comparative example]
LOS as a red phosphor (Kasei Optonics: KX-681), BAM: Eu, Mn (Kasei Optonics: KX-671) as a green phosphor, BAM (Kasei Optonics: KX-661) as a blue phosphor ) And aiming for CIE chromaticity (cx, cy) = (0.360, 0.365), the spectral fraction ratio was 66: 26: 8. Thereafter, a phosphor filter was produced in the same manner as in Example 1, and the emission characteristics were evaluated. As a result, Ra was 37.
[Examples 3 to 12]
The light emission characteristics were measured in the same manner as in Examples 1 and 2 with the compositions shown in Table 1. Among the phosphors used, the emission spectrum and excitation spectrum for Ca pyrophosphate and LOS are shown in FIGS. 4 to 14 for the other phosphors. Table 1 and FIGS. 15 to 18 show the results of evaluation of the light emission characteristics of Examples and Comparative Examples.
緑色蛍光体の(Sr,Ba)オルソ・シリケートについてはWLY450(インテマィックス社)を用いた。SrアルミネートおよびSrチオガレートの製造方法は以下の通りである。
[Srアルミネート:Sr0.8Al2O4:Eu0.2の合成 ]
SrCO3、Eu2O3およびαアルミナを0.8:0.1:1.0のモル比で計量した。均一混合した後、蓋付きアルミナ坩堝中で1200℃の温度で、3時間、H2を5%含むN2雰囲気下で焼成することにより合成した。
For the green phosphor (Sr, Ba) orthosilicate, WLY450 (Intemax Co.) was used. The production method of Sr aluminate and Sr thiogallate is as follows.
[Synthesis of Sr aluminate: Sr 0.8 Al 2 O 4 : Eu 0.2 ]
SrCO 3 , Eu 2 O 3 and α-alumina were weighed at a molar ratio of 0.8: 0.1: 1.0. After uniform mixing, the mixture was synthesized by firing in an alumina crucible with a lid at 1200 ° C. for 3 hours in an N 2 atmosphere containing 5% H 2 .
[Srチオガレート:Sr0.85Ga2S4:Eu0.15の合成 ]
Ga2S3、SrS、Eu2O3を1.0:0.85:0.075のモル比で計量した。均一混合した後、蓋付きアルミナ坩堝中で1000℃の温度で、8時間、N2雰囲気下で焼成することにより合成した。
[Synthesis of Sr thiogallate: Sr 0.85 Ga 2 S 4 : Eu 0.15 ]
Ga 2 S 3 , SrS, Eu 2 O 3 was weighed at a molar ratio of 1.0: 0.85: 0.075. After uniform mixing, the mixture was synthesized by firing in an alumina crucible with a lid at a temperature of 1000 ° C. for 8 hours in an N 2 atmosphere.
上記表1および図15〜18より、InGaN/GaN系半導体素子を用いた三波長型白色発光モジュールの赤色として、Caピロリン酸塩蛍光体を使用した場合、従来のLOSに対してRa、全光束共に向上することが明らかとなった。また、表1より、実施例1、4、7および10の結果から、青色発光蛍光体にCaアパタイトを用いた場合にRa、全光束共に優れていることが明らかとなった。 From Table 1 and FIGS. 15 to 18, when the Ca pyrophosphate phosphor is used as the red color of the three-wavelength white light emitting module using the InGaN / GaN-based semiconductor element, Ra, the total luminous flux is compared with the conventional LOS. It became clear that both improved. Further, from Table 1, from the results of Examples 1, 4, 7 and 10, it was revealed that both Ra and the total luminous flux are excellent when Ca apatite is used for the blue light emitting phosphor.
図4に示すように、Caピロリン酸塩は、600nm付近にピークを持ち、LOSよりブロードである。また、図5に示すように、励起スペクトルが近紫外線域でブロードであり、400nm付近では、LOSより励起スペクトルの相対強度が高いことが明らかである。 As shown in FIG. 4, Ca pyrophosphate has a peak in the vicinity of 600 nm and is broader than LOS. Further, as shown in FIG. 5, the excitation spectrum is broad in the near ultraviolet region, and it is clear that the relative intensity of the excitation spectrum is higher than that of LOS in the vicinity of 400 nm.
1 LEDチップ
2 リードフレーム
3 金属ワイヤー
4 蛍光体ペースト
5 封止材
1 LED chip 2 Lead frame 3 Metal wire 4 Phosphor paste 5 Sealing material
Claims (2)
Ca2-X-Y-ZMXP2O7:EuY,MnZ
(式中、MはCa以外のアルカリ土類元素を表し、X≧0、Y>0、Z>0である。)
前記一般式において、0.2≦Z/(Y+Z)≦0.8であり、
Caアパタイトである青色発光蛍光体と緑色発光蛍光体と前記橙色蛍光体とを含み、白色発光し、
前記橙色発光蛍光体(O)と前記緑色発光蛍光体(G)と前記青色発光蛍光体(B)の配合比率がスペクトル分率で、O:G:B=50〜60:20〜50:8〜30であることを特徴とする発光モジュール。 A light emitting module comprising a semiconductor element having an emission peak wavelength of 350 to 420 nm and a phosphor layer that emits light from the semiconductor element as an excitation light source, wherein the phosphor layer is represented by at least the following general formula an orange phosphor having an α-type Ca pyrophosphate crystal structure,
Ca 2-XYZ M X P 2 O 7: Eu Y, Mn Z
(In the formula, M represents an alkaline earth element other than Ca, and X ≧ 0, Y> 0, and Z> 0.)
In the general formula, Ri 0.2 ≦ Z / (Y + Z ) ≦ 0.8 der,
A blue light-emitting phosphor that is Ca apatite, a green light-emitting phosphor, and the orange phosphor;
The blending ratio of the orange-emitting phosphor (O), the green-emitting phosphor (G), and the blue-emitting phosphor (B) is a spectral fraction, and O: G: B = 50 to 60:20 to 50: 8. emitting module according to claim 30 der Rukoto.
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JP2009293022A (en) * | 2008-05-09 | 2009-12-17 | Mitsui Mining & Smelting Co Ltd | Green phosphor |
JP5390516B2 (en) * | 2008-05-19 | 2014-01-15 | 株式会社東芝 | LINEAR WHITE LIGHT SOURCE, BACKLIGHT AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME |
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CN115216296B (en) * | 2022-08-09 | 2023-10-24 | 烟台布莱特光电材料有限公司 | Synthetic method of efficient blue fluorescent powder for excitation of ultraviolet LED |
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